CN110336018A - A kind of modified nickel-cobalt lithium manganate material and its preparation method and application - Google Patents
A kind of modified nickel-cobalt lithium manganate material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of modified nickel-cobalt lithium manganate materials and its preparation method and application, nickel-cobalt lithium manganate material is added in the mixed solution of poly 4 vinyl pyridine and polyaniline, in the composite layer of nickel-cobalt lithium manganate material surface cladding polyaniline and poly 4 vinyl pyridine after drying, when the material is used as cell positive material, composite layer can not only reduce the contact area of positive electrode and electrolyte, inhibit the dissolution of transition metal in the electrolytic solution in positive electrode, hence it is evident that reduce the amount of dissolution of transition metal in electrolyte.And polyaniline has good electric conductivity in composite layer, and the electric conductivity of positive electrode is made to get a promotion, and thus battery made of material has good cycle performance and high rate performance.Poly 4 vinyl pyridine in composite layer can adsorb the transition metal element dissolved out from nickel-cobalt lithium manganate material, promote performance of lithium ion battery, prolong its service life, and security performance is better than simple nickle cobalt lithium manganate.
Description
Technical field
The invention belongs to field of lithium ion battery, and in particular to a kind of modified nickel-cobalt lithium manganate material and preparation method thereof and
Using.
Background technique
With the fast development of global economy and science and technology, the energy, environment, information become three big themes of social development,
Middle energy and environmental problem is by extensive concern all over the world.Lithium ion battery (LIBs) is as a kind of efficient green client
The energy is recycled.It has many advantages such as that operating voltage is high, specific energy is high, small in size, light-weight, the service life is long, wide
It is general to be used for the fields such as 3C, electric tool, model plane and new-energy automobile.Especially in new-energy automobile field, by the motorized of automobile
It is one of the revolutionary change of motor transport service instantly, in order to adapt to this change, lithium ion battery in a foreseeable future will
One of major technique selection as motorcar electric.With the lithium ion in portable electronic product and power grid storage battery market
Battery is compared, and electric car requires lithium ion battery to have higher service life and safety.
Positive electrode is one of the component part of most critical in LIBs, and the superiority and inferiority of performance directly constrains the property of LIBs
Energy.Currently, the LIBs positive electrode of the market mainstream has cobalt acid lithium, LiMn2O4, LiFePO4 and nickle cobalt lithium manganate.Especially nickel cobalt
Lithium manganate material, due to nickel, cobalt, three element of manganese coordinating effect, make its energy density, cycle performance, security performance and at
There is advantage in terms of the comprehensive performances such as this, be one of positive electrode of greatest concern at present.But in material there are transition metal
Nickel, cobalt, manganese are easy to dissolve in the electrolytic solution, and being migrated and being deposited on cathode SEI by electrolyte causes material electrochemical active
With can transmit the reduction of lithium ion, and then cause the decaying of LIBs performance.In recent years, main that performance of lithium ion battery is delayed to decline
The method subtracted has: (1) carrying out zwitterion substitution in nickle cobalt lithium manganate lattice, such as introduce the members such as Al, Mg, Zr, La, F, B
Element, to promote material lattice stability, (2) carry out coating on active material or electrode, reduce active material and electrolyte
Side reaction；(3) electrolysis additive promotes the stability of electrolyte.But the above method dissolves transition metal in the electrolytic solution
The problem of do not solve.
Summary of the invention
It is existing to solve the object of the present invention is to provide a kind of modified nickel-cobalt lithium manganate material and its preparation method and application
Transiting metal nickel, cobalt, manganese are easy the problem of dissolving in the electrolytic solution, causing LIBs performance degradation in technology.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of preparation method of modified nickel-cobalt lithium manganate material, comprising the following steps:
(1) nickel cobalt manganese presoma and lithium source are added to ball milling in ball grinder, obtain mixture；
(2) mixture obtains sintered sample after oversintering；
(3) sintering sample obtains nickel-cobalt lithium manganate material after Mechanical Crushing, sieving；
(4) by poly 4 vinyl pyridine, polyaniline dissolution solvent, stirring forms mixed serum；
(5) nickel-cobalt lithium manganate material in step (3) is added in the mixed serum in step (4), is stirred and ultrasonic,
It is dried to obtain anhydrous powder after mixing to get modified nickel-cobalt lithium manganate material is arrived.
Nickel cobalt manganese presoma is nickel, cobalt and manganese oxide, nickel cobalt manganese hydrogen-oxygen in the step (1) as a preferred technical solution,
One or more of compound or nickel cobalt manganese carbonate；The lithium source is lithium hydroxide, in lithium carbonate, lithium nitrate, lithium acetate
It is one or more of；Metal molar ratio 1.0:1.0~1.10 of the nickel cobalt manganese presoma and lithium source.
The revolving speed of ball grinder is 100-500r/min, the time of ball milling in the step (1) as a preferred technical solution,
For 0.5-3h, the medium of ball milling is polyurethane ball.
Sintering is divided into two stages of low temperature presintering knot and high temperature sintering in the step (2) as a preferred technical solution,；
Wherein the temperature of low temperature presintering knot is 300 DEG C -600 DEG C, time 3-10h；It is warming up to high temperature sintering after low temperature presintering knot,
The temperature of high temperature sintering is 700 DEG C -1000 DEG C, time 5-30h.
The atmosphere of the sintering is oxygen or air as a preferred technical solution,.
Sieving is sieving manually in the step (3) as a preferred technical solution, and the mesh number of sieve is 200-400 mesh.
As a preferred technical solution, in the step (4) poly 4 vinyl pyridine, polyaniline 1~2:1 of mass ratio,
The solvent is n,N-Dimethylformamide, and the mass fraction of solute is 5.0%~15% in mixed serum.
The mass ratio of nickel-cobalt lithium manganate material and mixed serum is in the step (5) as a preferred technical solution,
0.05~0.2:1；Dry temperature is 100 DEG C -120 DEG C, time 5-20h.
It is a further object to provide the modified nickel-cobalt lithium manganate materials as made from preparation method described above.
Third object of the present invention is to provide modification nickel-cobalt lithium manganate material described above as positive electrode in lithium
Application in ion battery.
The invention has the following advantages:
(1) nickel-cobalt lithium manganate material is added in the mixed solution of poly 4 vinyl pyridine and polyaniline by the present invention, is led to
It crosses drying evaporation solvent and works as nickel cobalt in the composite layer of nickel-cobalt lithium manganate material surface cladding polyaniline and poly 4 vinyl pyridine
When lithium manganate material is applied in lithium ion battery as positive electrode, composite layer not only reduces positive electrode and electrolyte
Contact area, and the dissolution of transition metal element in the electrolytic solution in positive electrode can be inhibited, hence it is evident that it reduces in electrolyte
The amount of dissolution of transition metal.And polyaniline has good electric conductivity in composite layer, proposes the electric conductivity of positive electrode
It rises, thus battery made of material has good cycle performance and high rate performance, after 200 weeks loop tests, battery
Capacity retention ratio is 92% or more.
(2) the functional functional group that poly 4 vinyl pyridine has in composite layer, can adsorb from nickel-cobalt lithium manganate material
The transition metal element of middle dissolution promotes performance of lithium ion battery, prolongs its service life.
(3) preparation method provided by the invention is easy to operate, and safe operation process is controllable, simple production process, Neng Goushi
Existing large-scale industrial production.
Detailed description of the invention
Fig. 1 is the circulation of battery made of modified nickel-cobalt lithium manganate material made from embodiment 1, embodiment 2 and comparative example 1
Performance map comparison diagram.
Specific embodiment
Below with reference to embodiment, the present invention will be further explained.Obviously, described embodiment is the present invention one
Section Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
Every other embodiment obtained under the premise of creative work out, shall fall within the protection scope of the present invention.
Embodiment 1
A kind of preparation method of modified nickel-cobalt lithium manganate material, includes the following steps.
Nickel cobalt manganese presoma Ni is weighed respectively0.5Co0.2Mn0.3(OH)2, battery-level lithium carbonate quality be respectively 1.0kg,
0.428kg, is added to ball milling mixing in ball grinder, rotational speed of ball-mill 200r/min, Ball-milling Time 1.5h, and ball-milling medium is poly- ammonia
Ester ball, obtains mixture.Then mixture is placed in tube furnace and is warming up to 550 DEG C with 5 DEG C/min of heating rate, low temperature is pre-
It is sintered 5h, then 900 DEG C of high temperature sintering 15h are warming up to 5 DEG C/min of heating rate, sintering atmosphere is air, naturally cools to room
Temperature, then by sintered sample Mechanical Crushing after cooling, manual 325 mesh sieving obtains nickel-cobalt lithium manganate material.
Material after above-mentioned sieving is added in the N,N-dimethylformamide solution that Solute mass fraction is 12% (poly-
4-vinylpridine, polyaniline mass ratio 1:1), simultaneously ultrasound 15min is stirred, mixed serum is formed.Then mixed serum is placed in
In vacuum oven, in 120 DEG C of dry 6h to get to modified nickel-cobalt lithium manganate material.
As shown in figure 1 and table 1, soft-package battery is made as positive electrode in above-mentioned modification nickel-cobalt lithium manganate material to pass through
Test discovery, discharge gram volume 163.4mAhg for the first time-1, capacity retention ratio 92.07% at circulation 200 weeks, cathode nickel after circulation,
Cobalt, manganese element changes of contents are respectively 145ppm, 89ppm, 156ppm.
Embodiment 2
A kind of preparation method of modified nickel-cobalt lithium manganate material, includes the following steps.
Nickel cobalt manganese presoma Ni is weighed respectively0.5Co0.2Mn0.3(OH)2, battery-level lithium carbonate be respectively 1.0kg,
0.428kg, is added to ball milling mixing in ball grinder, rotational speed of ball-mill 200r/min, Ball-milling Time 1.5h, and ball-milling medium is poly- ammonia
Ester ball, obtains mixture.Then mixture is placed in tube furnace and is warming up to 550 DEG C with 5 DEG C/min of heating rate, low temperature is pre-
It being sintered 5h, then 5 DEG C/min of heating rate rises to 900 DEG C of high temperature sintering 15h, sintering atmosphere is air, cooled to room temperature, then
By sintered sample Mechanical Crushing after cooling, manual 325 mesh sieving obtains nickel-cobalt lithium manganate material.
Above-mentioned nickel-cobalt lithium manganate material is added in the N,N-dimethylformamide solution that Solute mass fraction is 16%
(poly 4 vinyl pyridine, polyaniline mass ratio 1:1) stirs simultaneously ultrasound 15min, forms mixed serum.Then by mixed serum
It is placed in a vacuum drying oven, in 120 DEG C of dry 6h to get to modified nickel-cobalt lithium manganate material.
As shown in figure 1 and table 1, soft-package battery is made as positive electrode in above-mentioned modification nickel-cobalt lithium manganate material to pass through
Test discovery, discharge gram volume 162.6mAhg for the first time-1, capacity retention ratio 93.50% at circulation 200 weeks, cathode nickel after circulation,
Cobalt, manganese element changes of contents are respectively 128ppm, 76ppm, 133ppm.
Embodiment 3
A kind of preparation method of modified nickel-cobalt lithium manganate material, includes the following steps.
Nickel cobalt manganese presoma Ni is weighed respectively1/3Co1/3Mn1/3(OH)2, battery-level lithium carbonate quality be respectively 1.0kg,
0.432kg, is added to ball milling mixing in ball grinder, rotational speed of ball-mill 200r/min, Ball-milling Time 1.5h, and ball-milling medium is poly- ammonia
Ester ball, obtains mixture.Then mixture is placed in tube furnace and is warming up to 600 DEG C with 5 DEG C/min of heating rate, low temperature is pre-
It being sintered 5h, then 5 DEG C/min of heating rate is warming up to 960 DEG C of high temperature sintering 16h, sintering atmosphere is air, cooled to room temperature,
Again by sintered sample Mechanical Crushing after cooling, it is sieved manually, obtains nickel-cobalt lithium manganate material.
It is molten that nickel-cobalt lithium manganate material after above-mentioned sieving is added to the N,N-dimethylformamide that mass fraction is 12%
In liquid (poly 4 vinyl pyridine, polyaniline mass ratio 1:1), simultaneously ultrasound 15min is stirred, mixed serum is formed.It then will mixing
Slurries are placed in a vacuum drying oven, in 120 DEG C of dry 6h to get to modified nickel-cobalt lithium manganate material.
Embodiment 4
A kind of preparation method of modified nickel-cobalt lithium manganate material, includes the following steps.
Nickel cobalt manganese presoma Ni is weighed respectively0.6Co0.2Mn0.2(OH)2, battery-level lithium carbonate be respectively 1.0kg,
0.425kg, is added to ball milling mixing in ball grinder, rotational speed of ball-mill 200r/min, Ball-milling Time 1.5h, and ball-milling medium is poly- ammonia
Ester ball, obtains mixture.Then mixture is placed in tube furnace and is warming up to 500 DEG C with 5 DEG C/min of heating rate, low temperature is pre-
It being sintered 5h, then 5 DEG C/min of heating rate is warming up to 860 DEG C of high temperature sintering 13h, sintering atmosphere is oxygen, cooled to room temperature,
Again by sintered sample Mechanical Crushing after cooling, manual 325 mesh sieving obtains nickel-cobalt lithium manganate material.
Above-mentioned nickel-cobalt lithium manganate material is added in the N,N-dimethylformamide solution that Solute mass fraction is 12%
(poly 4 vinyl pyridine, polyaniline mass ratio 1:1) stirs simultaneously ultrasound 15min, forms mixed serum.Then by mixed serum
It is placed in a vacuum drying oven, in 120 DEG C of dry 6h to get to modified nickel-cobalt lithium manganate material.
Embodiment 5
A kind of preparation method of modified nickel-cobalt lithium manganate material, includes the following steps.
Nickel cobalt manganese presoma Ni is weighed respectively0.8Co0.1Mn0.1(OH)2, battery-level lithium carbonate quality be respectively 1.0kg,
0.425kg, is added to ball milling mixing in ball grinder, rotational speed of ball-mill 200r/min, Ball-milling Time 1.5h, and ball-milling medium is poly- ammonia
Ester ball, obtains mixture.Then mixture is placed in tube furnace and is warming up to 500 DEG C with 5 DEG C/min of heating rate, low temperature is pre-
It being sintered 5h, then 5 DEG C/min of heating rate is warming up to 760 DEG C of high temperature sintering 15h, sintering atmosphere is oxygen, cooled to room temperature,
Again by sintered sample Mechanical Crushing after cooling, manual 325 mesh sieving obtains nickel-cobalt lithium manganate material.
Above-mentioned nickel-cobalt lithium manganate material is added to (poly- 4- in the N,N-dimethylformamide solution that mass fraction is 12%
Vinylpyridine, polyaniline mass ratio 1:1), simultaneously ultrasound 15min is stirred, mixed serum is formed.Then mixed serum is placed in very
In empty drying box, in 120 DEG C of dry 6h to get to modified nickel-cobalt lithium manganate material.
Embodiment 6
A kind of preparation method of modified nickel-cobalt lithium manganate material, includes the following steps.
Nickel cobalt manganese presoma Ni is weighed respectively0.8Co0.1Mn0.1(OH)2, battery-level lithium carbonate quality be respectively 1.0kg,
0.425kg, is added to ball milling mixing in ball grinder, rotational speed of ball-mill 200r/min, Ball-milling Time 1.5h, and ball-milling medium is poly- ammonia
Ester ball, obtains mixture.Then mixture is placed in tube furnace and is warming up to 500 DEG C with 5 DEG C/min of heating rate, low temperature is pre-
It being sintered 5h, then 5 DEG C/min of heating rate is warming up to 760 DEG C of high temperature sintering 15h, sintering atmosphere is oxygen, cooled to room temperature,
Again by sintered sample Mechanical Crushing after cooling, manual 325 mesh sieving obtains nickel-cobalt lithium manganate material.
Above-mentioned nickel-cobalt lithium manganate material is added to (poly- 4- in the N,N-dimethylformamide solution that mass fraction is 12%
Vinylpyridine, polyaniline mass ratio 1:1), simultaneously ultrasound 15min is stirred, mixed serum is formed.Then mixed serum is placed in very
In empty drying box, in 120 DEG C of dry 6h to get to modified nickel-cobalt lithium manganate material.
Embodiment 6
A kind of preparation method of modified nickel-cobalt lithium manganate material, includes the following steps.
Nickel cobalt manganese presoma Ni is weighed respectively0.5Co0.2Mn0.3(OH)2, lithium nitrate quality be respectively 1.0kg, 0.428kg,
It is added to ball milling mixing in ball grinder, rotational speed of ball-mill 500r/min, Ball-milling Time 0.5h, ball-milling medium is polyurethane ball, is obtained
To mixture.Then mixture is placed in tube furnace and is warming up to 300 DEG C with 5 DEG C/min of heating rate, low temperature presintering knot
10h, then be warming up to 900 DEG C of high temperature sintering 30h with 5 DEG C/min of heating rate, sintering atmosphere are oxygen, cooled to room temperature,
Again by sintered sample Mechanical Crushing after cooling, manual 200 mesh sieving obtains nickel-cobalt lithium manganate material.
Material after above-mentioned sieving is added in the N,N-dimethylformamide solution that Solute mass fraction is 6% (poly-
4-vinylpridine, polyaniline mass ratio 2:1), simultaneously ultrasound 15min is stirred, mixed serum is formed.Then mixed serum is placed in
In vacuum oven, in 100 DEG C of dry 18h to get to modified nickel-cobalt lithium manganate material.
Comparative example 1
A kind of preparation method of nickel-cobalt lithium manganate material, includes the following steps.
Nickel cobalt manganese presoma Ni is weighed respectively0.5Co0.2Mn0.3(OH)2, battery-level lithium carbonate quality be respectively 1.0kg,
0.428kg, is added to ball milling mixing in ball grinder, rotational speed of ball-mill 200r/min, Ball-milling Time 1.5h, and ball-milling medium is poly- ammonia
Ester ball, obtains mixture.Then mixture is placed in tube furnace and is warming up to 550 DEG C with 5 DEG C/min of heating rate, low temperature is pre-
It being sintered 5h, then 5 DEG C/min of heating rate rises to 900 DEG C of high temperature sintering 15h, sintering atmosphere is air, cooled to room temperature, then
By sintered sample Mechanical Crushing after cooling, manual 325 mesh sieving obtains comparative example nickel-cobalt lithium manganate material.
As shown in figure 1 and table 1, soft-package battery is made by test using above-mentioned nickel-cobalt lithium manganate material as positive electrode
It was found that the gram volume 161.9mAhg that discharges for the first time-1.Capacity retention ratio 87.89% at circulation 200 weeks, cathode nickel, cobalt, manganese after circulation
Constituent content variation is respectively 246ppm, 152ppm, 268ppm.
The electric performance test technique of above-described embodiment often uses manufacture craft using market soft-package battery, has as follows:
(1) anode pole piece parameter: positive electrode, carbon black, binder mass percent be respectively 96.0%, 2.0%,
2.0%, compacted density 3.40g/cm3, surface density: 300g/cm2。
(2) cathode pole piece parameter: the mass percent point of carbonaceous mesophase spherules, sodium carboxymethylcellulose, binder, carbon black
Not Wei 94.0%, 2.0%, 2.5%, 1.5%, compacted density 1.40g/cm3, surface density: 145g/cm2。
(3) electrolyte: Zhuhai match dimension SW2080 type electrolyte.
(4) diaphragm: Ube 16um diaphragm.
The above-mentioned anode pole piece made, cathode pole piece, diaphragm, electrolyte are passed through into lamination, assembling, fluid injection, sealing, change
At processes such as, pumpings, it is made required Soft Roll, 20~40%, temperature is controlled 25 for Soft Roll production and test environment humid control
±3℃；It is that under the conditions of 1C/1C charge and discharge, the soft-package battery of production is subjected to circulation survey in 45 ± 2 DEG C of insulating boxs in temperature
Examination recycles 200 weeks.
Table 1 is 200 circulating cycles, battery capacity conservation rate and cathode transiting metal nickel, cobalt, manganese content variation at 45 DEG C
Table.As it can be seen from table 1 by the composite layer for coating polyaniline and poly 4 vinyl pyridine on nickle cobalt lithium manganate surface, for the first time
Discharge capacity increases, and is mainly attributed to conductive polyaniline clad and improves the electric conductivity of active material；Introduce cladding
After layer, capacity retention ratio is promoted to 92% or more from 87.89% when recycling 200 weeks, and cycle performance obviously gets a promotion, cyclicity
The promotion of energy and the dissolution reduction of transiting metal nickel, cobalt, manganese, which have, directly to be contacted, and the 4-vinylpridine in composite layer can adsorb
The transition metal element dissolved out from nickel-cobalt lithium manganate material, so cycle performance be improved significantly.
200 circulating cycle battery capacity conservation rates and cathode transiting metal nickel, cobalt, manganese content change table at 1:45 DEG C of table.
Claims (10)
1. a kind of preparation method of modified nickel-cobalt lithium manganate material, it is characterised in that: the following steps are included:
(1) nickel cobalt manganese presoma and lithium source are added to ball milling in ball grinder, obtain mixture；
(2) mixture obtains sintered sample after oversintering；
(3) sintered sample obtains nickel-cobalt lithium manganate material after Mechanical Crushing, sieving；
(4) poly 4 vinyl pyridine, polyaniline are dissolved in solvent, stirring forms mixed serum；
(5) nickel-cobalt lithium manganate material in step (3) is added in the mixed serum in step (4), is dried after mixing
Anhydrous powder is obtained to get modified nickel-cobalt lithium manganate material is arrived.
2. preparation method according to claim 1, it is characterised in that: nickel cobalt manganese presoma is nickel cobalt in the step (1)
One or more of Mn oxide, nickel cobalt manganese hydroxide or nickel cobalt manganese carbonate；The lithium source is lithium hydroxide, carbonic acid
One or more of lithium, lithium nitrate, lithium acetate；The nickel cobalt manganese presoma and the metal molar ratio 1.0:1.0 of lithium source~
1.10。
3. preparation method according to claim 1, it is characterised in that: the revolving speed of ball grinder is 100- in the step (1)
500r/min, the time of ball milling are 0.5-3h, and the medium of ball milling is polyurethane ball.
4. preparation method according to claim 1, it is characterised in that: sintering is divided into low temperature presintering knot in the step (2)
With two stages of high temperature sintering；Wherein the temperature of low temperature presintering knot is 300 DEG C -600 DEG C, time 3-10h；Low temperature presintering junction
High temperature sintering is warming up to after beam, the temperature of high temperature sintering is 700 DEG C -1000 DEG C, time 5-30h.
5. the preparation method according to claim 4, it is characterised in that: the atmosphere of the sintering is oxygen or air.
6. preparation method according to claim 1, it is characterised in that: sieving is sieving manually, sieve in the step (3)
Mesh number be 200-400 mesh.
7. preparation method according to claim 1, it is characterised in that: poly 4 vinyl pyridine, polyphenyl in the step (4)
1~2:1 of mass ratio of amine, the solvent are n,N-Dimethylformamide, in mixed serum the mass fraction of solute be 5.0%~
15%.
8. preparation method according to claim 1, it is characterised in that: nickel-cobalt lithium manganate material and mixed in the step (5)
The mass ratio for closing slurries is 0.05~0.2:1；Dry temperature is 100 DEG C -120 DEG C, time 5-20h.
9. modified nickel-cobalt lithium manganate material made from preparation method a method as claimed in any one of claims 1-8.
10. application of the modified nickel-cobalt lithium manganate material as positive electrode in lithium ion battery as claimed in claim 9.
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Denomination of invention: A modified lithium nickel cobalt manganate material and its preparation method and Application Effective date of registration: 20220714 Granted publication date: 20220531 Pledgee: Hefei science and technology rural commercial bank Limited by Share Ltd. Shushan branch Pledgor: HEFEI RONGJIE ENERGY MATERIALS CO.,LTD. Registration number: Y2022980010493 |